Process of desulfurizing crude petroleum.



No. 738,656. PATENTED SEPT. 8, 1903.-

A. W. BURWELL & L. O. SHERMAN. V

PROCESS OF DESULFURIZING CRUDE PETROLEUM;

APP LIGATION FILED FEB. 27, 1903.

'NO MODEL.

llNiTsn STAT S Patented September 8, 1903.

PATENT @FFTQE.

ARTHUR W. BURWELL AND LAYTON O. SHERMAN, OF CLEVELAND, OHIO; SAID BURVVELL ASSIGNOR TO SAID SHERMAN.

PROCESS OFDESULFURIZING CRUDE PETROLEUM.

SFECIFICATION forming part of Letters Patent No. 738,656, dated September 8, 1903.

Application filedIebrusi-y 2'7, 1903.

To all whom it may concern.-

Be it known that we,ARTHUR W. BURWELL and LAYTON O. SHERMAN, citizens of the United States, residing at Cleveland, in the county of Cuyahoga and State of Ohio, have iuvented certain new and useful Improveerablyin admixture. It is important to the success of the process that both the vapors of oil and the mixture of iron oxid and lime should be entirely free from water, either combined or physically held. The partiallydesulfurized vapors are then condensed and the distillate is subjected to the usual treatment with sulfuric acid and caustic alkali, whereby the percentage of sulfur in the oil is reduced to a minimum.

The process may be carried out by the use of widely-different forms of apparatus. One,

which has been found suitable for the purpose is shown in the accompanying drawing, in which the figure is a vertical longitudinal section through the heating-furnace, still, and chamber containing the iron oxid and lime.

The still 1 may be of any usual construction, that shown being a horizontal cylinder of boiler-iron set in a furnace having a firegrate 2, fuel and ash-pit doors 3 4, and stack 5. An outlet 6 for the vapors leads from the top of the still near its rear end. From the side of this outlet leads a branch pipe 7.

Upon the rear portion of the still is supported a chamber 8, containing a series of horizontal foraminous shelves 9, of perforated iron or heavy wire-cloth. The shelves are arranged as bafiles, alternate shelves extending from opposite ends of the chamber, so that the vapors rising from'the still pass back and forth between the shelves, as well as through the shelves, before they escape from the chamber through the outlet 10 in its upper Serial No. 145,319. (No specimens- The crude oil in the still is now heated until vapors begin to escape through outlet 6. As it is important that the vapors which pass through chamber 8 to be treated by the material therein shall be entirely free from water, a valve in pipe 7 (not shown) is opened and the slide-valve 1 1, which covers outlet 6, is closed, so that the first portions of the oilvapors which contain water escape through pipe '7. As soon as the water in the charge of oil has been entirely distilled 05 the valve in pipe Fis closed and the slide-valve 11 is opened, so that the water-free vapors pass through the chamber 8 and over and through the shelves and the treating materials carried upon them. The temperature of the materials in chamber 8 is merely high enough to prevent condensation of the oil-vapors,.

and this temperature is readily maintained without special heating means by the heat of the vapors. themselves and by the'proximity of the chamber to the still. Thejron oxid and quicklime directly remove a considerable portion of the sulfur in the oil, but in general not enough to render it commercially available. The vapors from outlet 10 are condensed and the distillate is subjected to the usual treatment with sulfuric acid and caustic alkali. This second treatment practically removes all of the sulfur from the oil or reduces it to the desired minimum. The reagents in chamber 8 seem to break up the sulfur compounds in the oil and to not only remove a portion of the sulfur, but to bring the remaining portion into a condition where it is readily removed by the usual acid-and-alkali treatment.

(Jalcined dolomite entirely free from water or other alkaline-earth oxid may be substiforth.

tuted for quicklime, and any anhydrous iron oxid may be employed, although the sesquioxid is most available.

We are aware that others have proposed already to desnlfurize oil-vapors by bringing them in contact with either iron oxid or lime. Our invention contemplates the use of both water-free iron oxid and quicklime, thejoint action of the two reagents being required.

We claim- 1. The process of desulfurizing crude petroleum, which consists in distilling the petroleum, and passing the oil-vapors in contact with oxids of iron and an alkaline-earth metal, both of said oxids being entirely free from water, as set forth.

2. The process of desulfurizing crude petroleum, which consists in distilling the petroleum, and passing the oil-vapors in contact with a mixture of finely-divided oxids of iron and an alkaline-earth metal, both of said oxids being entirely free from water, as set 3. The process of 'desulfurizing. crude petroleum, which consists in distilling the petroleum, rejecting the first portions of the vapor containing water, and passing the other oil-vapors in contact with water-free oxids of iron and an alkaline-earth metal, as set forth.

4. The process of desulfurizing crude petroleum; which, consists in distilling the petroleum, rejecting the first portions of the vapor containing water, and passing the other oil-vapors in contact with a mixture of finelydivided, water-free oxids of iron and an alkaline-earth metal, as set forth. 7

5. The process'ofldesulfurizing crude petroleum, which consists in distilling thepetroleum, passing the oil-vapors in contact with oxids of iron and an alkaline-earthmetal, both of said oxids being entirely free from water, condensing the treated vapors, and subjecting the distillate to the usual treatment with acid and alkali, as set forth.

6. The process of desulfurizing crude petroieum, which consists in distilling the petroleum, passing the oil-vapors in contact with a mixture of finely-divided oxids of iron and an alkaline-earth metal,both of said oxids being entirely free from water, condensing troleum, which consists in distilling the petroleum, rejecting the first portions of the vapor containing water, passing the other oilvapors in contact with water-free oxids of iron and an alkaline-earth metal, condensing the treated vapors, and subjecting the distill- 6o late to the usual treatment with acid and alkali, as set forth. 7 j

8. The process of desnlfurizing crude petroleum, which consists in distilling the petroleum, rejecting the first portions of the vapor containing water, passing the other oilvapors in contact with a mixture of finelydivided, watenfree oxids of iron and an alkal'ine-earth metal, condensing the treated vapors, and subjecting the distillate to the usual treatment with acid andalkali, as set forth. v 9. The process of desulfurizing crude petroleum, which consists in distilling the petroleum, and passing the oil-vapors in contact with oxids of iron and-an alkaline-earth metal, both of said oxids being entirely free from water, maintained at a low temperature, merely sufficient to prevent condensation of the vapors, as set forth.

10. The process of desulfurizing crude petroleum, which consists in distilling the petroleum, and passing the oil-vapors in contact with a mixture of finely-divided oxids of iron and an alkaline-earth metal,both of said oxids being entirely free from water, maintained at a low temperature, merely sufiicient to prevent condensation of the vapors,ras set forth.

In testimony whereof we afix our signatures in presence of two witnesses.

ARTHUR W. BURWELL. LAYTON O. SHERMAN.

Witnesses:

Cass. E. BAKER, A. O. BOWEN. 

